CN116240544A - Pvd复合cvd的金刚石涂层制备方法及所制成的涂层和刀具 - Google Patents
Pvd复合cvd的金刚石涂层制备方法及所制成的涂层和刀具 Download PDFInfo
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Abstract
本发明公开了一种PVD复合CVD的金刚石涂层制备方法及所制成的涂层和刀具，涂层包括CVD金刚石层和PVD过渡层，PVD过渡层设置在基体表面，CVD金刚石层设置在PVD过渡层表面，PVD过渡层包括底层的Cr层、中间的CrN层和表层的Cr层。基体表面沉积PVD过渡层，PVD过渡层表面沉积CVD金刚石层，PVD过渡层能够阻挡基体中的Co扩散，能够提高CVD金刚石层与基体之间的结合力，改善涂层的力学性能。本发明可广泛应用于涂层制备技术领域。
Description
技术领域
本发明涉及涂层制备技术领域，特别涉及一种PVD复合CVD的金刚石涂层制备方法及所制成的涂层和刀具。
背景技术
硬质合金刀具因其高弹性模量、高导热系数和宽的工作温度范围而在机械加工行业中得到广泛应用。然而，在切割铝合金、绿色陶瓷和研磨性复合材料时，它们的磨损率很高。新材料的发展应用需要新刀具的开发研究。金刚石具有高硬度、高耐磨性、低摩擦系数和化学惰性等，应用于硬质合金刀具涂层，可以极大提高硬质合金刀具的寿命及切削效率，且在其它方面也具有非常广阔的发展应用前景。
但大部分CVD金刚石涂层存在膜/基结合力差的问题，这极大地制约了金刚石涂层的应用。导致该现象的原因有：沉积中基体Co扩散至表面，催化石墨形成，导致结合降低；沉积后的迅速冷却，由于金刚石与基体间热膨胀系数不匹配导致热压缩应力。因此如何提高金刚石膜/基附着力、断裂韧性等一直是该领域的亟需解决的问题。
发明内容
为解决上述技术问题中的至少之一，本发明提供一种PVD复合CVD的金刚石涂层制备方法及所制成的涂层和刀具，所采用的技术方案如下。
本发明所提供的PVD复合CVD所制成的涂层包括CVD金刚石层和PVD过渡层，所述PVD过渡层设置在基体表面，所述CVD金刚石层设置在PVD过渡层表面，所述PVD过渡层包括底层的Cr层、中间的CrN层和表层的Cr层。
本发明的某些实施例中，表层的所述Cr层厚度为200至250nm，底层的所述Cr层厚度为200至250nm，所述PVD过渡层的厚度为1至3μm。
本发明的某些实施例中，所述CrN层设置为至少一层。
本发明的某些实施例中，所述基体设置为高速钢、硬质合金、陶瓷、金属陶瓷、立方氮化硼和Si中的一种。
本发明所提供的PVD复合CVD所制成的刀具的表面沉积如权利要求1至4任一项所述的涂层。
本发明所提供的PVD复合CVD的金刚石涂层制备方法包括如下工作流程：
将基体抛光清洗；
将基体装载至反应腔中；
反应腔室抽真空，加热，对基体进行离子清洗、刻蚀；
通入氩气，利用物理气相沉积技术在基体上沉积Cr层；
通入氮气与氩气，利用物理气相沉积技术在Cr层上沉积一层或多层CrN层；
通入氩气，利用物理气相沉积技术在CrN层上沉积Cr层；
经过清洗、金刚石植晶后，采用CVD技术在PVD过渡层上制备金刚石层。
本发明的某些实施例中，所述Cr层通过如下步骤沉积得到，开启装有Cr靶的HiPIMS电源，向真空室通入氩气100sccm至200sccm，控制真空室气压为0.4Pa至2Pa；将基体的偏压设置为-100V至-200V，功率设置为1kW至5kW，频率设置为200至500Hz，脉冲宽度为50至250μs。
本发明的某些实施例中，沉积时间为5min至20min。
本发明的某些实施例中，采用HFCVD或PECVD技术在PVD过渡层上制备金刚石层。
本发明的某些实施例中，底层的Cr层厚度为200至250nm，表层的Cr层厚度为200至250nm，PVD过渡层的厚度为1至3μm。
本发明的实施例至少具有以下有益效果：基体表面沉积PVD过渡层，PVD过渡层表面沉积CVD金刚石层，PVD过渡层能够阻挡基体中的Co扩散，能够提高CVD金刚石层与基体之间的结合力，改善涂层的力学性能。本发明可广泛应用于涂层制备技术领域。
附图说明
本发明的实施例所描述和/或所附加的方面和优点，结合下面附图将变得明显和容易理解。应说明的是，下面附图所体现的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
图1为对比例1中采用HFCVD于上沉积的金刚石涂层(a)与实施例1中于Cr/CrN/Cr上沉积的金刚石涂层(b)的表面和截面扫描电镜图的对比。
图2为对比例1的金刚石涂层和实施例1的金刚石涂层纳米压痕测试结果图。
图3为对比例1的金刚石涂层和实施例1的金刚石涂层在维氏压痕测试后的扫描电镜图。
图4为本发明中PVD复合CVD所制成的涂层的结构示意图。
具体实施方式
下面结合图1至图4详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
在本发明的描述中，需要理解的是，若出现术语“中心”、“中部”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，除非另有说明，“多个”的含义是两个或两个以上。
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。
本发明涉及一种PVD复合CVD所制成的刀具，刀具表面沉积涂层。
刀具的其他构成以及操作对于本领域普通技术人员而言在相关技术中已有记载，这里不再详细描述，以下将对涂层的结构展开介绍。
本发明涉及一种PVD复合CVD所制成的涂层，涂层包括CVD金刚石层和PVD过渡层，PVD过渡层设置在基体表面，CVD金刚石层设置在PVD过渡层表面，PVD过渡层包括底层的Cr层、中间的CrN层和表层的Cr层。
作为一种实施方式，PVD过渡层的厚度为1至3μm，PVD过渡层较薄，沉积在刀具表面不会影响刀具的形状，且有利于保证刀具切削刃的锐利。
一些示例中，PVD过渡层厚度设置为2μm。为测试PVD过渡层的厚度对Co扩散的阻挡效果，采用HiPIMS制备了0.8μm和2μm的PVD过渡层，后续在HFCVD下沉积金刚石层，0.88μm的PVD过渡层上出现金刚石层掉膜，且EDS能够检测到基体的Co元素，而2μm的PVD过渡层上金刚石层无掉膜，表面光滑平整。
作为一种实施方式，底层的Cr层厚度为200至250nm，增加CrN层与基体的结合力，在沉积过程中也可与扩散的Co元素发生化合。
作为一种实施方式，CrN层设置为至少一层，提供良好的扩散阻挡作用和承载能力，同时作为中间层缓解金刚石层与基体间的热膨胀系数不匹配所带来的问题，降低涂层的内应力。
一些示例中，CrN层设置为1.6μm。
作为一种实施方式，表层的Cr层厚度为200至250nm。可以理解的是，表层的Cr层在碳扩散下容易达到碳饱和，且碳在Cr中的扩散相对较低，Cr层作为金刚石的形核生长界面，有利于金刚石的形核生长，效果比Al、Ti等金属更好。
作为一种实施方式，基体设置为高速钢、硬质合金、陶瓷、金属陶瓷、立方氮化硼和Si中的一种。
本发明涉及一种PVD复合CVD的金刚石涂层制备方法，金刚石涂层制备方法包括如下工作流程：
将基体抛光清洗；
将基体装载至反应腔中；
反应腔室抽真空，加热，从室温加热至450℃，对基体进行离子清洗、刻蚀，去除污染物；
通入氩气，利用物理气相沉积技术在基体上沉积Cr层；
通入氮气与氩气，利用物理气相沉积技术在Cr层上沉积一层或多层CrN层；
通入氩气，利用物理气相沉积技术在CrN层上沉积Cr层；
经过清洗、金刚石植晶后，采用CVD技术在PVD过渡层上制备金刚石层。
进一步地，Cr层通过如下步骤沉积得到，开启装有Cr靶的HiPIMS电源，向真空室通入氩气100sccm至200sccm，控制真空室气压为0.4Pa至2Pa；将基体的偏压设置为-100V至-200V，功率设置为1kW至5kW，频率设置为200至500Hz，脉冲宽度为50至250μs。进一步地，沉积时间为5min至20min。
一些示例中，底层的Cr层厚度为200至250nm，表层的Cr层厚度为200至250nm，PVD过渡层的厚度为1至3μm。
一些示例中，采用HFCVD或PECVD技术在PVD过渡层上制备金刚石层。
可以理解的是，PVD过渡层形成Cr/CrN/Cr多层结构，能够起到阻挡基体Co的扩散，以使金刚石涂层不受基体中Co含量的影响，提高膜/基结合力。PVD过渡层所形成的软金属层有利于金刚石的植晶效率，促进CVD金刚石层沉积时的形核密度和生长。采用HiPIMS技术所制备的PVD过渡层结构更致密、表面质量更好，能够更加有效阻挡沉积过程中Co扩散，所制备获得的涂层结合力高，且无明显缺陷。
底层的Cr层能够有效提高CrN层与基体间的结合力，且能够偶遇扩散出来的Co反应形成化合物，阻挡基体Co的扩散，且由于Cr层较薄，因此能够减小Cr层对PVD过渡层整体的力学性能影响。
PVD过渡层中的CrN层具有良好的热稳定性，在CVD金刚石层沉积过程中能够有效阻止Co的扩散，且采用HiPIMS制备的CrN硬度可高达24GPs，能够提供良好的力学性能支撑，并能够缓解金刚石层与基体的热膨胀系数不匹配所带来的影响，降低涂层的内应力。其中金刚石涂层的热膨胀系数为0.8×10-6K，基体的热膨胀系数为6×10-6K。
PVD过渡层表面的Cr层一方面有利于碳的扩散形成碳化物界面，例如形成Cr3C2或Cr7C3，碳化物界面的形成与金刚石的形核生长有关。另一方面，表层的Cr层能够提高金刚石层与过渡层之间的结合力。
本发明所设计的金刚石涂层制备方法可取代传统的制备方法，能够避免传统制备方式下的化学刻蚀对基体所造成的破坏，通过沉积PVD过渡层的方式取代金刚石沉积前的化学蚀刻和热处理等前处理工艺，处理方式更加简单便捷易控制，工艺适应性好，产品一致性更好，PVD过渡层更加有利于金刚石植晶和形核生长，能够有效提高金刚石层与基体之间的结合力，获得理学性能、表面质量更佳的金刚石涂层。
下面结合具体的实施例详细描述本发明的内容，应注意的是，下述描述仅为示例性说明，而不是对本发明的具体限制。
对比例1
基体选用硬质合金，采用常规的化学蚀刻对基体进行拔钴处理，消除钴对沉积的不利影响，基体完成酒精清洗、金刚石植晶等前处理步骤，随后采用HFCVD在基体表面沉积MCD/NCD金刚石涂层。
实施例1
基体选用硬质合金，超声清洗、烘干后，基体装载至涂层炉的反应腔中，加热和抽真空至设定条件，对基体进行离子清洗。
通入氩气，开启离子源，离子源的功率设定为2kW，调整偏压为-400V、气压为0.6Pa，对基体进行离子轰击，设定离子轰击的时长为15min。
关闭离子源，通入氩气，开启Cr靶，HiPIMS电源功率为4kw、电压为700V、频率500Hz、脉宽100μs、偏压为-100V、气压为0.7Pa，设定沉积时间为7min，沉积Cr层，涂层厚度约200nm。
同时通入氩气与氮气，氩气流量为85sccm，氮气流量为40sccm，HiPIMS电源参数不变，偏压为-100V、气压为0.7Pa，设定沉积时间为70min开始沉积CrN层，涂层厚度约2μm。
停止通入氮气，改变通入的氩气量，HiPIMS电源参数不变，偏压为-100V、气压为0.7Pa设定沉积时间为7min，沉积Cr层，涂层厚度约200nm。
经过上述步骤获得具有Cr/CrN/Cr三层结构的涂层，涂层硬度为15.7GPa。
取出样品，经过酒精清洗、金刚石植晶处理后，在HFCVD下沉积MCD/NCD金刚石涂层。
如图1所示，无PVD过渡层的样品经过化学蚀刻后沉积的金刚石涂层在6k倍的电镜下表面粗糙度更大，存在明显的高低不平，存在大量缺陷；而镀有Cr/CrN/Cr过渡层的金刚石涂层表面在低倍下非常平整，表面无明显缺陷。
如图2所示，利用纳米压痕对两组样品的硬度与弹性模量进行测试，可以发现有Cr/CrN/Cr过渡层的样品的硬度及弹性模量比传统方式制备的金刚石涂层硬度高约10GPa。
如图3所示，采用维氏压痕对无过渡层与Cr/CrN/Cr过渡层上的金刚石涂层进行压痕实验，测试力为1000gf，保载时间为20s。可以看到无过渡层的金刚石涂层样品边缘的裂纹更多，而Cr/CrN/Cr过渡层上的金刚石涂层样品裂纹较少，说明实施例1所制成的涂层韧性更好。
如图4所示为实例1中涂层的结构示意图，基体上为PVD过渡层，底层的Cr层用于提高基体与氮化物层的结合力；氮化物层提高力学支撑、阻挡扩散及缓解热应力等作用；表层的Cr层由于提高氮化物层与金刚石的结合力，也可以起到促进金刚石植晶、形核生长的作用。
实施例2
基体选用硬质合金，超声清洗、烘干后，基体装载至涂层炉的反应腔中，加热和抽真空至设定条件，对基体进行离子清洗。
通入氩气，开启离子源，离子源的功率设定为2kW，调整偏压为-400V、气压为0.6Pa，对基体进行离子轰击，设定离子轰击的时长为15min。
关闭离子源，通入氩气，开启Cr靶，HiPIMS电源功率为4kw、电压为700V、频率500Hz、脉宽100μs、偏压为-100V、气压为0.7Pa，设定沉积时间为7min，沉积金属Cr层，涂层厚度约200nm。
同时通入氩气与氮气，氩气流量为60sccm，氮气流量为85sccm，HiPIMS电源参数不变，偏压为-100V、气压为0.7Pa，制备CrN涂层，涂层厚度约1.8μm。
停止通入氮气，改变通入的氩气量，HiPIMS电源参数不变，偏压为-100V、气压为0.7Pa设定沉积时间为7min，沉积Cr层，涂层厚度约200nm。
经过上述步骤获得具有Cr/CrN/Cr的三层涂层，其硬度为17.2GPa。
取出样品，经过酒精清洗、金刚石植晶处理后，在HFCVD下沉积MCD/NCD金刚石涂层。
在本说明书的描述中，若出现参考术语“一个实施例”、“一些实例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上结合附图对本发明的实施方式作了详细说明，但是本发明不限于上述实施方式，在所述技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。
本发明的描述中，专利名称若出现“、”，表示“和”的关系，而不是“或”的关系。例如专利名称为“一种A、B”，说明本发明所要求保护的内容为：主题名称为A的技术方案和主题名称为B的技术方案。
Claims (10)
1.一种PVD复合CVD所制成的涂层，其特征在于：包括CVD金刚石层和PVD过渡层，所述PVD过渡层设置在基体表面，所述CVD金刚石层设置在PVD过渡层表面，所述PVD过渡层包括底层的Cr层、中间的CrN层和表层的Cr层。
2.根据权利要求1所述的PVD复合CVD所制成的涂层，其特征在于：表层的所述Cr层厚度为200至250nm，底层的所述Cr层厚度为200至250nm，所述PVD过渡层的厚度为1至3μm。
3.根据权利要求1或2所述的PVD复合CVD所制成的涂层，其特征在于：所述CrN层设置为至少一层。
4.根据权利要求1所述的PVD复合CVD所制成的涂层，其特征在于：所述基体设置为高速钢、硬质合金、陶瓷、金属陶瓷、立方氮化硼和Si中的一种。
5.一种PVD复合CVD所制成的刀具，其特征在于：所述刀具的表面沉积如权利要求1至4任一项所述的涂层。
6.一种PVD复合CVD的金刚石涂层制备方法，其特征在于：所述金刚石涂层制备方法制备如权利要求1至4任一项所述的涂层，所述金刚石涂层制备方法的工作流程包括
将基体抛光清洗；
将基体装载至反应腔中；
反应腔室抽真空，加热，对基体进行离子清洗、刻蚀；
通入氩气，利用物理气相沉积技术在基体上沉积Cr层；
通入氮气与氩气，利用物理气相沉积技术在Cr层上沉积一层或多层CrN层；
通入氩气，利用物理气相沉积技术在CrN层上沉积Cr层；
经过清洗、金刚石植晶后，采用CVD技术在PVD过渡层上制备金刚石层。
7.根据权利要求6所述的PVD复合CVD的金刚石涂层制备方法，其特征在于：所述Cr层通过如下步骤沉积得到，开启装有Cr靶的HiPIMS电源，向真空室通入氩气100sccm至200sccm，控制真空室气压为0.4Pa至2Pa；将基体的偏压设置为-100V至-200V，功率设置为1kW至5kW，频率设置为200至500Hz，脉冲宽度为50至250μs。
8.根据权利要求7所述的PVD复合CVD的金刚石涂层制备方法，其特征在于：沉积时间为5min至20min。
9.根据权利要求6至8任一项所述的PVD复合CVD的金刚石涂层制备方法，其特征在于：采用HFCVD或PECVD技术在PVD过渡层上制备金刚石层。
10.根据权利要求6至8任一项所述的PVD复合CVD的金刚石涂层制备方法，其特征在于：底层的Cr层厚度为200至250nm，表层的Cr层厚度为200至250nm，PVD过渡层的厚度为1至3μm。
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